Process for the production of water-insoluble azo dyestuffs on textile material of cellulose or protein fibers



United States Patent M 3,484,181 PROCESS FOR THE PRQDUTEON 0F WATER-IN- SGLUBLE AZU DYESTUFFS 0N TEXTTLE MATE- REAL 0F CELLULGSE 0R PROTEIN FIBERS Hasso Hertel and Werner Kirst, Offenbach (Main), Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed Feb. 18, 1965, Ser. No. 433,783 Claims priority, application Germany, Feb. 22, 1964, F 42,093; Mar. 7, 1964, F 42,232; July 8, 1964, F 43,370; July 25, 1964, F 43,563

Int. Cl. C09b 43/16 U5. Cl. 8-45 4 Claims ABSTRACT 0F THE DISCLOSURE A process for preparing water-insoluble azo dyestuffs on textile material of cellulose or protein fibers comprising treating the textile material in an alkaline bath which contains a coupling component, a diazoamino compound of the formula wherein R represent phenyl, halogenophenyl, alkylphenyl, alkoxyphenyl, dialkylphenyl, alkylhalogenophenyl, alkoxyhalogenophenyl, alkylcarbamylphenyl, alkoxycarbamylphenyl, alkylsulfamylphenyl, alkoxysulfamylphenyl, alkyl(alkylor aralkyl-sulfonyl) phenyl, alkoxy (alkylor aralkyl-sulfonyl) phenyl or acylaminophenyl, Alk represents lower straight or branched chain alkyl which may be substituted by carboxyl, and R represents carboxyalkyl, sulfoalkyl or sulfophenyl which may be substituted by a halogen atom or alkyl, a wetting or dispersing agent and, optionally, a mineral salt, and then causing formation of the dyestuff by a treatment with acid agents in the same bath at temperatures below 40 C.

The present invention provides a process for the production of water-insoluble azo dyestuffs on textile material of cellulose or protein fibers.

It has been found that water-insoluble azo dyestuffs can be produced on textile material of cellulose or protein fibers by treating the textile material in an alkaline bath which contains a coupling component and a diazoamino compound of the Formula 1 Alk in which R represents phenyl, halogenophenyl, alkylphenyl, alkoxyphenyl, dialkylphenyl, alkylhalogenophenyl, alkoxyhalogenophenyl, alkylcarbamylphenyl, alkoxycarbamylphenyl, alkylsulfamylphenyl, alkoxsulfamylphenyl, alkyl(alkylor aralkyl-sulfonyl) phenyl, alkoxy (alkylor aralkyl-sulfonyl) phenyl or acylaminophenyl, Alk represents lower straight or branched chain alkyl which may be substituted by carboxyl, and R represents carboxyalkyl, sulfoalkyl or sulfophenyl which may be substituted by a halogen atom or alkyl, furthermore a wetting or dispersing agent and, if desired, a mineral salt, and then causing formation of the dyestuff by a treatment with acid agents at temperatures below 40 C.

The process of the present invention is carried out by treating the textile material in the form of yarn hanks, wound bodies, slubbings or piece goods in an alkaline bath which contains a coupling component having high substantivity and a diazo-amino compound of the indicated composition as Well as a wetting or dispersing 3,484,181 Patented Dec. 16, 1969 agent and, if desired, a mineral salt, for example, sodium chloride, sodium phosphate or sodium sulfate. The treatment is carried out for at least 10 minutes in order to ensure that the coupling component is sufficiently and uniformly fixed onto the textile material. In general, the process is carried out at temperatures between about 10 and about 35 C., suitably at room temperature or at a slightly elevated temperature. When the coupling component is essentially fixed and has levelled, an organic acid, for example, formic acid, acetic acid, tartaric acid, citric acid, lactic acid or glycollic acid, a mixture of these acids, a mixture of a mineral acid, for example, hydrochloric acid or sulfuric acid, with an organic acid or a mixture of a mineral acid with the salt of an organic acid, is added to the bath in a quantity such that the total quantity of alkali in the bath and on the textile material is neutralized and a pH-value of between about 4 and 7 is reached.

The pH-value required for obtaining optimum dyestuff yield depends, above all, on the diazoamino compound of the Formula 1 used. For example, in the case of compounds in which R is alkoxyhalogenophenyl or alkylhalogenophenyl the pH-value is at about 5, in the case of compounds in which R is alkoxycarbamylphenyl it is at about 5, in the case of compounds in which R is alkoxysulfamylphenyl at about 4 and in the case of compounds in which R is acylaminophenyl it is at about 6.

The temperature required for the dyestuff formation is in the range of between about 10 and about 40 C. After the formation of the dyestuff on the textile material has taken place, the material is subsequently washed in a neutral or acid bath, if desired or required in the presence of dispersing agents, and the dyeing is further treated in the usual manner. In this manner, dyeings are obtained which exhibit very good fastness to rubbing.

Piece goods can be dyed in the following manner: the goods are impregnated on a two or multiple roller foulard with a mixture of the coupling component and an excess of diazoamino compound, the goods are wound up and after a period of stay of, for example, half an hour, coupling is effected at temperatures below 40 C. by passing the goods through an organic acid, a mixture of organic acids or a mixture of organic and mineral acids. This dyestuff development may be effected by a single passage in a compartment of a roller vat or by several passages in a jigger or winch beck; the addition of mineral salts and dispersing agents during impregnation and development may sometimes have a very advantageous effect. In this method of operation, the concentration of the coupling component in the initial bath must be lower in comparison to that of the second bath, corresponding to the higher afiinity of the coupling component, whereas the concentration of the diazoamino compound in the initial bath compared to that of the second bath is not to be reduced. This method of operation saves energy; intermediate drying of the dyestufi prior to the development of the dyestuff is not required.

As coupling components, there may be used in the process of the present invention compounds which are distinguished by a high substantivity towards the textile material used, i.e. coupling components, which at a goods to liquor ratio of 1:20, a dyeing period of 30 minutes, at 30 C., a concentration of 1 g. per liter of water, without addition of salt and with an excess of 4.5 g. of sodium hydroxide per liter of bath, have so high a substantivity that at least 9 g. are absorbed on 1 kg. of cotton. Suitable compounds are, for example, 2,3-hydroxynaphthoyl-aminobenzenes such as 1-(2,3'- hydroxynaphthoylamino) 2,5 dimethoxy-4-chlorobenzene or 1-(2',3'-hydroxynaphthoylamino)-2-methoxy-4- chloro-S-methylbenzene, 6-bromoor 6-methoxy-2,3-hydroxynaphthoic acid aryl amides such as 1-(6'-bromo- 2',3 hydroxynaphthoylamino)-2-methoxybenzene, condensation products of 2,3-hydroxynaphthoic acid and oligonuclear isocyclic or heterocyclic amines such as 2- (2,3' hydroxynaphthoylamino)-naphthalene, 2-(2,3'- hydroxynaphthoylamino) carbazole, 2 (2'3-hydroxynaphthoylamino) 3-methoxy-diphenylene oxide, 6-(2',3- hydroxynaphthoylamino) benzimidazole, 6 (2',3'-hydroxynaphthoylamino) indazole, -(2,3'-hydroxynaphthoylamino)-2-methylbenzthiazole or 4 (23-hydroxynaphthoylamino)-diphenyl and the substitution products thereof, 4,4 bis(2",3 hydroxynaphthoylamino) diphenyl and the substitution products thereof such as 4,4- bis (2",3 hydroxynaphthoylamino)-3,3-dimethoxydiphenyl, 1,4-bis-(2",3"-hydroxynaphthoylamino)benzene and the substitution products thereof, 4,4-bis-(2,3"-hydroxynaphthoylamino)-stilbene, 4,4-bis-(2",3 hydroxynaphthoylamino)-azobenzene and the substitution products thereof, 4,4'-bis-(2",3"-hydroxynaphthoylamino)-diphenyl urea, 2-hydroxyanthracene-3-carboxylic acid aryl amides such as 1-(2-hydr0xyanthracene-3'-carboylamino) 2 methylbenzene, 2 hydroxycarbazole-3-carboxylic acid aryl amides such as l-(2'-hydroxycarbazole- 3' car-boylamino)-4-chlorobenzene, 5-hydroxy-l,2,1',2- benzocarbaZole-4-carboxylic acid arylamides such as 1- (5 hydroxy 1,2, 1",2"-benzocarbazole-4'-carboylamino)-4-methoxybenzene or 1-(5-hydroxy-1',2,1,2- benzocarbazole 4-carboylamino)-2-methyl-4-methoxybenzene, or terephthaloyl-bisacetic acid aryl amides such as terephthaloyl bis (1-acetylamino-2,4-dimethoxy-5- chl0robenzene)- or terephthaloyl-bis-(l-acetylamino-2- methoxy-4-chloro-5-methylbenzene) As diazoamino compounds, there may especially be used compounds obtained by coupling diazotized aniline, diazotized chloroanilines, toluidines, anisidines, xy-lidines, chlorotoluidines, chloroanisidines or dazotized aminoalkoxybenzoic acid amides, aminoalkoxyzenzene-sulfonic acid amides, aminoalkylbenzenesulfonic acid amides or aminoalkylbenzoic acid amides which may be substituted in the amide group by alkyl or aryl radicals, diazotized aminoalkylphenyl (alkyl or aralkyl)-sulfones, aminoalkoxyphenyl (alkylor aralkyl)-sulfones or monoacylated phenylene-diamines, with the alkali metal salts or alkalin'e earth metal salts of N-alkylated aliphatic a, 18- or amino-carboxylic acids, for example, N-(methyl)-aminoacetic acid, N-(butyl)-,8-aminopropionic acid, N-propylfiaminobutyric acid or N-(methyl)-a-aminopropionic acid, of N-alkyltaurines, especially of N-methyltaurine, of imidodiacetic acid, of an iminodipropionic acid or iminodibutyric acd, or of N-alkysulfanlic acids which may be substituted by a halogen atom or by an alkyl group.

As wetting or dispersing agents, there may be used the compounds conventionally used in ice colour technique, for example, condensation products of higher molecular fatty acids and protein degradation products, condensation products of higher molecular fatty acids and aminoalkysulfonic acids, condensation products of formaldehyde with naphthalene-sulfonic acids, or purified sulfite cellulose waste liquor.

The process can be applied to textile material of natural or regenerated cellulose, cyanoethylated cellulose, wool, natural silk or regenerated protein fibers.

Compared with the usual dyeing methods with ice colours, the process of the present invention is considarably simpler. In the known dyeing methods, the dyebath is usually drained after the impregnation with the coupling component, the goods are centrifuged, separated with suction or rinsed intermediately and the dyestufr is developed with a diazonium compound in a second bath. [n contradistinction thereto, in the process of the present invention impregnation and development are carried out 31 one bath and after the period of stay required for fixing the coupling component, coupling is effected without any other intercalated operation, which saves operational time to a considerable degree.

It is generally known that diazoamino compounds of diazotized aromatic amines and N-(methyl)-aminoacetic acid, iminodiacetic acid, N-methyltaurine or N-alkyl-sulfanilic acids may be used for the production of azo dyestuffs on the fiber, by printing such diazoamino componds in admixture with coupling components on the material and developing the dyestuffs by a treatment with acids. This process is at present widely used in industry. However, it has not been known as yet and, in view of the state of the art, it was very surprising that such mixtures can also be used for the dyeing of fibers in any processing stages, even of wound bodies, without intermediate drying of the goods.

It is known that water-insoluble azo dyestuffs can be produced on vegetable fibers by treating these fibers at long goods to liquor ratios with a bath containing a coupling component and a diazo or tetrazoamino compound without hydrosolubilizing groups and subsequently developing the azo dyestuif by treatment with an acid bath (German Patent 1,057,061).

In comparison with this process, the process of the present invention, which is carried out with substantive coupling components and diazoamino compounds of the indicated Formula 1 is distinguished by the fact that the development of the dyestuffs can be effected at low temperatures and that it is not necessary to raise the temperature after the addition of acid. Another advantage of the process of the present invention is that the diazoamino compound with aliphatic aminocarboxylic acids as stabilizers are present in the bath in the form of dissolved alkali metal salts, which ensures complete penetration of the material to be dyed and thus complete coupling, whereas, if water-insoluble diazoamino compounds are used, these compounds are only deposited on the surface of the material to be dyed which turns out in unsatisfactory dyeings and fastness to rubbing.

The following examples illustrate the invention, but they are not intended to limit it thereto:

EXAMPLE 1 A cross-wound bobbin of 500 g. of cotton was treated for 30 minutes at 30 C. on a dyeing apparatus in the following bath:

7 g. of 2-(2',3'-hydroxynaphthoylamino)-naphthalene were dissolved in 14 cc. of denatured ethyl alcohol, 7 cc. of water having 60 C., 2.8 cc. of a 38 B. sodium hydroxide solution and 3.5 cc. of a 33% formaldehyde solution, and introduced into a bath containing 5 g. of a condensation product obtained from an aminoalkylsulfonic acid and a higher molecular fatty acid, 30 cc. of a 38 B. sodium hydroxide solution, 42 g. of trisodium phosphate, 25 g. of sodium chloride and 16.3 g. of the diazoamino compound of diazotized I-amino-Z-methoxy- 4-benzoylamino-5-methylbenzene and the sodium salt of N-(methyl)-aminoacetic acid in 5 liters of water having 30 C. 75. cc. of a 50% acetic acid were added and the treatment was carried on for 30 minutes. The bobbin was then rinsed hot and cold and treated for 15 minutes, at 60 C., with 12.5 g. of a mixture of 63% of perchloroethylene, 17% of a reaction product of about 10 mols of ethylene oxide and 1 mol of nonyl phenol and 20% of isopropyl alcohol and 2.5 g. of the sodium salt of nitrilotriacetic acid in 5 liters of water, was then rinsed, soaped for 15 minutes at boiling temperature with 5 g. of a condensation product of an aminoalkylsulfonic acid and a higher molecular fatty acid and 2.5 g. of the sodium salt of nitrilotriacetic acid in 5 liters of water, rinsed and dried. A red violet dyeing having very good properties of fastness was obtained.

EXAMPLE 2 Cotton yarn was treated, at a goods to liquor ratio of 1:20, for 30 minutes, at 30 C., in the following bath:

3 g. of 1-(2',3'-hydroxynaphthoylamino)-2-methoxy-4- chloro-S-methylbenzene were dissolved in 6 cc. of de- Diazoamino compound of methyltaurine-sodium and diazotized Coupling component Tint 1-amin0-2-chl0robenzene 2-(2,g-hydroxynaphthoylamino)-8-rnethoxydiphenylene Red brown. X1 e. 1-amino-2-chloro-4-benzoyl-amino-E-methoxy-benzene l-(gl, 3-hydr0xynaphthoy1-amino)-2, 'dirnethoxy-4-chloro- Dark violet.

8117,6118. 1-arnino-2, 5dimet11oxy4-benzoylaminobenzene 2-(2,g-hydroxynaphthoy1-amino)-3-methoxy-diphenylene- Dark blue. 0x1 e. 1-amino2, idimethoxy-S-benzoylaminobenzene d0 Dark violet. l-amino-2-methyl-4-eh10robenzene 1(2, 3-l1ydroxynaphthoyl-amrno) -2-methoxy-4-chloro-5- Red.

methylbenzene.

Red.

l-amino-2-methyl-5-ch1orobenzene Red 1-amino-2-methoxybenzene-5-carboxylic acid amide 2-(2, 3-hydroxynapl1thoyl-amino)-naphthalene B ordeanx.

imethoxyi-chlorol-amino-Z-meth oxy-5-chlorob enzene 1-amino-2, e-dimethyl-5 benzoylaminobenzen do ed.

1-amino-2-methoxy-4-benzoylamino-5-methylbe 2-(2,g-hyd.roxynaphthoyl-amino) 3-methoxy-diphenylene Brownish Bordeaux.

l-amino-Z-methoxy-benzene-5-sulf0nic acid dicthylamide 2-(2,3 hydroxynaphthoyl-amino)-naphthalene Red. l-aminc-2-methoxybenzene-5-sulfonic acid dimethyl amide Z-(g, 3-hydroxynaphthoyl-amino)-2, 5-dimethoxy-4-cl1loro- Yellowish red.

enzone. 1-amin0-2-methoxy-benzene-5-carboxylic acid phenyl amide. Lg, 3-hydroxynaphthoylamino) -2, 5dimethoxy-4-oh1oro- Do.

enzene. l-amino-hnethoxy-fi-benzylsulfonylbenzene 2-(2,g-hydroxynaphthoylamino)-3-methoxydiphenylene- Red.

on e. 1-amino-2-methyl-3-chlorobenzene 1-(2-hydr0xycarbazole-3-carboylamino)-4-chlorobenzene Red brown. l-aminobenzene 2-(2,3-hyd.roxynaphthoylamino)-naphthalene Scarlet. 1-amino-2-methylb enzene "do D o. l-amino-Z-methoxybenzene .do Bordeaux.

EXAMPLE 5 g. of sodium chloride and 2.35 g. of the diazoamino Cotton on cross-wound bobbins was treated, at a goods compound of the formula to liquor ratio of 1:10, for half an hour, at 2530 C., in a bath containing, per liter of liquor, 1 g. of the sodi- (IJHS um salt of ethylenendiarninotetracetic acid, 1 g. of a condensation product of oleic acid and methyltaurine, 6.4 O 2 Nab cc. of a sodium hydroxide solution of 38 B., 1.1 g. of A) 2-(2,3'-hydroxynaphthoylamino) naphthalene, 30 g. of CH3 sodium chloride and 2.25 g. of the diazoamino compound of the formula After half an hour, 11 cc. of 50% acetic acid were added per liter of bath and the fabric was further treated for about 30 minutes. The fabric was then rinsed and soaped CH3 as indicated in Example 1. A Bordeaux dyeing was obtained which was fast to rubbing.

I The process was carried out as described in Example 01 3, but using 1.85 of the diazoamino compound of the formula After half an hour, 11.5 cc. of 50% acetic acid per liter of bath were added and the yarn was further treated for half an hour. The yarn was then rinsed and soaped each QN:N N (CH COON)3 time for 15 minutes at 60 C. and at the boiling temperature, with a solution containing per liter of water, 1 CONE g. of a condensation product of oleic acid and methyltaurine and 0.5 g. of the sodium salt of nitrilotriacetic acid, A r y ing Was obtained wh was fast to rubbingrinsed and dried. A red dyeing was obtained which was EXAMPLE 9 fast to rubbing. C no t t d t d t 1, h o n yarn was reae a a goo s o rquor ra 10 or EXAMPLE6 1:20, at 25-30 C., in a bath containing, per liter of h process was i d t as d ib d i Example liquor, 1 g. of the sodium salt of ethylenediaminotetracet- 1, but using 2.4 g. of the diazoamino compound of the i0 acid, 1 g. of a condensation product of oleic acid and formula methyl-taurine, 7.5 cc. of a sodium hydroxide solution of 38 B., 1 g. of 2-(2,3-hydroxynaphthoylaanino)-3-methoxydiphenylene oxide, 20 g. of sodium chloride, and CH3 2.15 g. of the diazoamino compound of the formula I C N=NN( CHz-CH3C O 0 Na);

I OGHa C1 N=NN( CHO OONa):

G5 I A red dyeing was obtained which was fast to rubbing. S OTOZHS EMMPLE 7 A knitted fabric of cotton was treated, at a goods to After half an hour, a mixture of 6.35 cc. of hydrochloric liquor ratio of 1:20 for 30 minutes, at 30 C., in a bath acid of 20 B. and 6 cc. of 50% acetic acid was added, containing, per liter of liquor, 1 g. of the sodium salt of per liter of bath, and dyeing was continued for about half ethylenediaminotetracetic acid, 1 g. of a condensation an hour. The yarn was then rinsed, soaped each time for product of oleic acid and methyltaurine, 6.5 cc. of a 15 minutes, at 60 C. and at 95 C., with a solution consodium hydroxide solution of 38 B., 1 g. of 2-(2,3'- taining, per liter of water, 1 g. of condensation product of hydroxynaphthoylamino)-3-methoxy diphenylene oxide, oleic acid and methyltaurine, 0.5 g. of the sodium salt of l3 l4 nitrilotriacetic acid and 0.5 g. of sodium carbonate, rinsed amides of terephthaloyl-bis-acetic acid, (2) a diazoamino and dried. A red dyeing was obtained which was fast to compound having the formula:

rubbing.

EXAMPLE 10 1TRl 2 Cotton yarn was treated, at a goods to liquor ratio of 5 1:20, for 15 minutes at 30 C., in the following bath: 1 in Which R is a member Selected from the group Consistg. of 2- (2',3'-hydroxynaphthoylamino) -3 -methoxy-dig f p y ehlerophenyl, lower y p y lower phenylene oxide was dissolved in 2 cc. of denatured ethyl alkOXY P 31 (ii-lower y p y lower alkylchloroalcohol, 0.5 cc. of sodium hydroxide solution of 38 B., P y lower alkOXY chlofophenyl, lower alkoxycafbamyland 2 cc. of water having 70 C., and introduced into a P y lOWer y- -(p y y p y lower bath containing 2.17 g. of a 30% diazoamino compound y ynf y p y lower yof diazotized l-amino-2-methyl-5-chlorobenzene and the chloro-benloylamiflophenyl, lower yy y sodium salt of N-methylsulfanilic acid, 1 g. of a conden- P y and lower alkoXy-lowel alkysulfonylphenyl, Z psation product of oleic acid and rnethyl-taurine and 7 cc. resents member selected from the group Consisting of of sodium hydroxide solution of 38 B. The bath was lower alkyl and 10W61' alkylene-coo (alkali and then made up to 1 liter by means of water. g. of 1 is a member selected from the group consisting f sodium chloride were then added, and the yarn was lower illkylelle-coo (alkali lower y a further treated for 15 minutes, 10.6 cc. of 50% acetic (alkali mflal) and acid were added and the treatment was continued for minutes. The yarn was then rinsed, soaped each time for 20 s 15 minutes at 60 C. and at 95 C. with a solution containing, per liter of water, 1 g. of condensation product (alkali metal), d a disp rsing agent, and Subseof oleic acid and methyl-taurine and 0.5 g. of the sodium quently, without an intermediate drying step, treating salt of nitrilo-triacetic acid, rinsed and dried. A red dye- Said textile materials in the same bath at temperatures ing having very good properties of fastness was obtained. of between about 10 C. and about C. with an acid When, in the above example, 4.02 g. of a 16.4% diazoagent selected from the group consisting of organic acids, amino compound of diazotized l-amino 2 -methy1-5- inorganic acids and mixtures thereof in such an amount chlorobenzene and the sodium salt of N-ethyl-sulfanilic that in the bath and on the textile material a pH value acid, or 4.75 g. of a 16.3% diazoamino compound of dietween about 4 and 7 is achieved.

azotized l-amino -2-methoxybenzene-S-carboxylic acid 30 2. Th P C as Claimed in Claim wherein a 101 amide and the sodium salt of N-ethyl-sulfanilic acid were p ng Component selected from the group consisting of used instead of the diazoamino compound of diazotized 2-(2',3'-hydroxynaphthoylamino)-naphthalene, 1 (2,3'- 1-amino-2-methyl-5-chlorobenzene and the sodium salt of hydroxynaphthoylamino)-2-methoxy 4 chloro-S-methyl- N-methyl-sulfanilic acid, red dyeings having very good benzene, '5' hydroxynaphthoylamino)-4-Cl1l0r0be11- properties of fastness were obtained. 39 zene, 1-(2,3'-hydroxynaphthoylamino)-2,5-dimethoxy-4- When, in the above example, 0.74 g. of 2-(2,3-hychlorobenzene, 2-(2',3' hydroxynaphthoylamino)-3-medroxynaphthoylamino)-naphthalene and 30 g. of sodium thoXy-diphenylene oxide, 1-(2-hydroxycarbazole-3'-carchloride, were used instead of 1 g. of 2-(2',3'-hydroxy- 0y 1 in0)- -Cl1l0r0benZene, 1 (5-hydroxy-l',2',l",2- naphthoylamino) 3 methoxy-diphenylene oxide, a yel- 4O benzocarbazole-4-carboylamino)-4-methoxybenzene and lowish red dyeing having good properties of fastness was terephthaloyl bis (1-acetylamino-2-methoxy-4-chloro-5- obtained, methylbenzene) is employed.

Diazoarnino compound of the sodium salt of N- ethylsulfanilic acid and diazotized Coupling comp nent Tint l-arnin0-2-methoxybenzene-zE-carboxylic acid amide- 1-(2,3-hydroxyn phtholy min )-2,5- imethoxyA-chlorobenzene Vivid red. l-arnino-Q-rncthyl-3-chlorobenzene 2-(2,3-hydroxynaphthoyl mm )naphthalene Scarlet. 1-arnin0-2-metl1oxybenzene-5-Suli0nic acid diethyl d0 Red.

amide. l-amino-2-methyl-3-ch10robenzene 1-(2-hydroxycarbaz0le-3-carboylamlnu)-4-chlorobenzene Brown;

Do 1-(5-hydr0xy-l', 2, l". 2"-benz(marl)flZ0le4-CarbOylamin0)-4-meth0xybenzene Blnish r d.

The above table indicates a number of other com- 3. The process as claimed in claim 1, wherein an inponents which may be used according to the present in- Organlc salt 18 ad d 0 the alkallne bath. vention and the tints of the azo dyestuffs produced on The P as clalmed 1n clalm 3, Whfifeln a Salt selected from the group consisting of sodium chloride,

sodium phosphate and sodium sulfate is employed.

References Cited UNITED STATES PATENTS cellulose fibers.

We claim:

1. A process for producing water-insoluble azo dyestuffs on cellulose and protein textile materials which comprises treating said textile materials at temperatures 1,382,560 10/1932 Glietellburg et between about 10 C. and about 35 C. in an aqueous 3; 3 1 13 0 am ers alkaline bath WhlCh contains (1) a couplln component 2,926,986 3/1960 Petitcolas et a 8 45 which is highly substantive for the textile material employed, said component being selected from the group GEORGE LESMES, Primary Examiner consisting of arylamides of aromatic oitho-hydroxy car- T. J. HERBERT, JR., Assistant Examiner boxylic acids, arylarnides of heterocyclic ortho-hydroxy US. Cl. X.R. carboxylic acids, arylarnides of acyl acetic acids and aryl- 

